This is a study on electrolytes that takes a thermodynamically consistent coupling between mechanics and diffusion into account. It removes some inherent deficiencies of the popular Nernst-Planck model. A boundary problem for equilibrium processes is used to illustrate the features of the new model.

We propose a modeling framework for magnetizable, polarizable, elastic, viscous, heat conducting, reactive mixtures in contact with interfaces. To this end, we first introduce bulk and surface balance equations that contain several constitutive quantities. For further modeling of the constitutive quantities, we formulate constitutive principles. They are based on an axiomatic introduction of the entropy principle and the postulation of Galilean symmetry. We apply the proposed formalism to derive constitutive relations in a rather abstract setting. For illustration of the developed procedure, we state an explicit isothermal material model for liquid electrolyte|metal electrode interfaces in terms of free energy densities in the bulk and on the surface. Finally, we give a survey of recent advancements in the understanding of electrochemical interfaces that were based on this model.

We consider the contact between an electrolyte and a solid electrode. At first we formulate a thermodynamic consistent model that resolves boundary layers at interfaces. The model includes charge transport, diffusion, chemical reactions, viscosity, elasticity and polarization under isothermal conditions. There is a coupling between these phenomena that particularly involves the local pressure in the electrolyte. Therefore the momentum balance is of major importance for the correct description of the boundary layers. The width of the boundary layers is typically very small compared to the macroscopic dimensions of the system. In the second step we thus apply the method of asymptotic analysis to derive a simpler reduced bulk model that already incorporates the electrochemical properties of the double layers into a set of new boundary conditions. With the reduced model, we analyze the double layer capacitance for a metal-electrolyte interface.

A priori and a posteriori error estimates are derived for the numerical approximation of scalar and complex valued phase field models. Particular attention is devoted to the dependence of the estimates on a small parameter and to the validity of the estimates in the presence of topological changes in the solution that represents singular points in the evolution. For typical singularities the estimates depend on the inverse of the parameter in a polynomial as opposed to exponential dependence of estimates resulting from a straightforward error analysis. The estimates naturally lead to adaptive mesh refinement and coarsening algorithms. Numerical experiments illustrate the reliability and efficiency of this approach for the evolution of interfaces and vortices that undergo topological changes.

Electron transfer reactions are commonly described by the phenomenological Butler-Volmer equation which has its origin in kinetic theories. The Butler-Volmer equation relates interfacial reaction rates to bulk quantities like the electrostatic potential and electrolyte concentrations. Although the general structure of the equation is well accepted, for modern electrochemical systems like batteries and fuel cells there is still intensive discussion about the specific dependencies of the coefficients. A general guideline for the derivation of Butler-Volmer type equations is missing in the literature. We derive very general relations of Butler-Volmer structure which are based on a rigorous non-equilibrium thermodynamic model and allow for adaption to a wide variety of electrochemical systems. We discuss the application of the new thermodynamic approach to different scenarios like the classical electron transfer reactions at metal electrodes and the intercalation process in lithium-iron-phosphate electrodes. Furthermore we show that under appropriate conditions also adsorption processes can lead to Butler-Volmer equations. We illustrate the application of our theory by a strongly simplified example of electroplating.